US4349471A - Process for the preparation of aromatic sulphonic acid halides - Google Patents

Process for the preparation of aromatic sulphonic acid halides Download PDF

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Publication number
US4349471A
US4349471A US06/227,445 US22744581A US4349471A US 4349471 A US4349471 A US 4349471A US 22744581 A US22744581 A US 22744581A US 4349471 A US4349471 A US 4349471A
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acid
aromatic
process according
sulphonic acid
chloride
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Heinz U. Blank
Erich Wolters
Norbert Langenfeld
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Bayer AG
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Bayer AG
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Assigned to BAYER AKTIENGESELLSCHAFT,A CORP. OF GERMANY reassignment BAYER AKTIENGESELLSCHAFT,A CORP. OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BLANK HEINZ U., LANGENFELD NORBERT, WOLTERS ERICH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides

Definitions

  • the invention relates to a process for the simultaneous preparation of aromatic sulphonic acid halides and aromatic carboxylic acid halides or the corresponding carboxylic acids by reaction of aromatic sulphonic acids with aromatic trihalogenomethyl compounds in the presence of a Bronsted acid or Lewis acid.
  • a process has now been found for the simultaneous preparation of aromatic sulphonic acid halides and aromatic carboxylic acid halides or of the corresponding carboxylic acids by reaction of an aromatic sulphonic acid or sulphonic acid anhydride with an aromatic trihalogenomethyl compound, which is characterised in that at least half an equivalent of an aromatic trihalogenomethyl compound is reacted per equivalent of sulphonic acid, in the presence of a Bronsted acid or Lewis acid at a temperature of 20°-300° C., if appropriate in an inert solvent.
  • aromatic sulphonic acids which can be employed in the process according to the invention are those of the general formula ##STR1## in which X represents hydrogen, ##STR2## wherein Y represents --O--, --SO 2 --, --N ⁇ N-- or --CH 2 and R 1 , R 2 , R 3 , R 1' and R 2' independently of one another denote hydrogen, alkyl, cycloalkyl, aryl, aralkyl, hydroxyl, alkoxy, acyloxy, halogen, acylamino, N-carbalkoxyamino.
  • two of the radicals R 1 , R 2 and R 3 which are adjacent can be part of a fused-on cycloaliphatic or aromatic ring which is optionally substituted by a sulphonic acid group.
  • aromatic trihalogenomethyl compounds which can be employed for the process according to the invention are those of the general formula ##STR3## in which U represents hydrogen, ##STR4## wherein V represents --O--, --SO 2 --, --N ⁇ N-- or --CH 2 --,
  • R 4 , R 5 , R 6 , R 4' and R 5' independently of one another denote hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, CHal 3 , halogen, isocyanato, N-carbalkoxyamino or N-carbaryloxyamino and, furthermore,
  • R 4 , R 5 and R 6 which are adjacent can be part of a fused-on cycloaliphatic or aromatic ring which is optionally substituted by CHal 3 , and
  • Hal represents chlorine or bromine.
  • alkyl which may be mentioned are straight-chain or branched hydrocarbon radicals with 1 to 6, preferably 1 to 4 and particularly preferably 1 to 2, carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl.
  • cycloalkyl examples include cyclopentyl and cyclohexyl, preferably cyclohexyl.
  • aryl which may be mentioned are aromatic carbocyclic radicals such as phenyl, naphthyl and anthryl, preferably phenyl, i.e. compounds having 6 to 18 carboxylic carbon atoms.
  • aralkyl examples include hydrocarbon radicals with 1 to 6 carbon atoms in the aliphatic part and 6 to 14 carbon atoms in the aromatic part, such as benzyl, ⁇ -phenyl-ethyl, naphthylmethyl, naphthylethyl, anthrylmethyl, ⁇ -phenyl-propyl and ⁇ -phenyl-n-hexyl.
  • Benzyl is the preferred aralkyl.
  • alkoxy which may be mentioned are straight-chain or branched radicals of aliphatic alcohols with 1 to 6, preferably 1 to 4 and in particular 1 to 2, carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy and hexyloxy.
  • Aryloxy which may be mentioned are radicals of aromatic hydroxy compounds with 6 to 14 carbon atoms, such as phenoxy, naphthyloxy and anthryloxy, preferably phenoxy.
  • halogen examples include fluorine, chlorine, bromine and iodine, preferably fluorine, chloride and bromine and particularly preferably chlorine and bromine.
  • two of the radicals R 1 to R 3 or R 4 to R 6 which are adjacent can be parts of a fused-on cycloaliphatic or aromatic ring
  • the benzene nucleus of the formula (I) or of the formula (II) the indane, indene, tetrahydronaphthalene and naphthalene system.
  • the preferred fused ring systems are the naphthalene system and the tetrahydronaphthalene system. The naphthalene system is particularly preferred.
  • R 7 , R 8 and R 9 independently of one another denote hydrogen, C 1-C 4 -alkyl, phenyl, benzyl, methoxy, ethoxy, phenoxy, fluorine, chlorine, bromine, nitro or the sulphonic acid group,
  • two of the radicals R 7 to R 9 which are adjacent can be part of a fused-on cycloaliphatic or aromatic 6-membered ring.
  • Aromatic sulphonic acids which may be mentioned as particularly preferred for the process according to the invention are those of the general formula ##STR6## in which R 10 and R 11 independently of one another denote hydrogen, methyl ethyl, chlorine or fluorine,
  • R 10 and R 11 if they are adjacent, can be part of a fused-on cycloaliphatic or aromatic 6-membered ring.
  • R 10 or R 11 when R 10 or R 11 are part of a cycloaliphatic ring, it preferably has 4 to 12 carbocyclic carbon atoms. Cycloalkane rings are particularly contemplated.
  • aromatic sulphonic acids examples which may be mentioned are: benzenesulphonic acid, 2-, 3- and 4-toluenesulphonic acid, 2-, 3- and 4-chloro-benzenesulphonic acid, 2,5- and 3,4-dichloro-benzenesulphonic acid, benzene-1,3-disulphonic acid, 2-chloro-toluene-4-sulphonic acid, 4-chloro-toluene-2-sulphonic acid, toluene-2,4-disulphonic acid, 1-acetylamino-benzene-4-sulphonic acid, 4-carbomethoxyamino-benzenesulphonic acid, 1- and 2-naphthalene-sulphonic acid, naphthalene-1,5-, 2,6- and 2,7-disulphonic acid, 4-biphenylsulphonic acid, 4,4'-biphenyl-disulphonic acid, 4-phenoxy-benzenesulphonic acid,
  • Aromatic trichloromethyl compounds may be mentioned in particular as aromatic trihalogenomethyl compounds for the process according to the invention.
  • Examples of trichloromethyl compounds are those of the general formula ##STR7## in which R 12 , R 13 and R 14 independently of one another denote hydrogen, chlorine, trifluoromethyl or trichloromethyl,
  • two of the radicals R 12 to R 14 which are adjacent can be parts of a fused-on cycloaliphatic or aromatic 6-membered ring.
  • radicals R 15 and R 16 if they are adjacent, can be parts of a fused-on cycloaliphatic or aromatic 6-membered ring.
  • trichloromethyl compounds may be mentioned as examples, benzotrichloride, 1-chloro-2-trichloromethylbenzene, 1-chloro-4-trichloromethylbenzene, 2,4-dichloro-1-trichloromethylbenzene, 1,3-bis-(trichloromethyl)-benzene, 1,4-bis-(trichloromethyl)-benzene, 1-trichloromethyl-naphthalene, 2-trichloromethylnaphthalene, 4-trichloromethyl-biphenyl, 4,4'-bis-(trichloromethyl)-biphenyl, 4-trichloromethyl-diphenyl ether, 4-trichloromethyl-diphenyl-methane, benzotribromide, 1-bromo-2-tribromomethylbenzene and 1-bromo-4-tribromomethylbenzene.
  • reaction of aromatic sulphonic acids of the formula (III) with aromatic trichloromethyl compounds of the formula (V) is preferred, and the reaction of sulphonic acids of the formula (IV) with trichloromethyl compounds of the formula (VI) is particularly preferred.
  • a Bronsted acid is in general characterised in that it contains a dissociable hydrogen atom
  • a Lewis acid is in general characterised in that it has a gap for an electron pair (in this context, see text book of theoretical chemistry, for example H. A. Staab, Einbowung in die theoretician organische Chemie (Introduction to Theoretical Organic Chemistry), 3rd Edition, page 599 et seq., Verlag Chemie, Weinheim 1962).
  • Bronsted acids for the process according to the invention are sulphuric acid, pyrosulphuric acid, phosphoric acid, pyrophosphoric acid and the acid salts of these acids, and furthermore polyphosphoric acid, fluorosulphonic acid, chlorosulphonic acid and bromosulphonic acid.
  • Lewis acids for the process according to the invention are aluminum chloride, iron chloride, zinc chloride, cadmium chloride, mercury-II chloride, beryllium chloride, magnesium chloride, boron trifluoride, boron trichloride, gallium chloride, titanium dichloride, titanium tetrachloride, zirconium tetrachloride, nickel chloride, niobium pentachloride, uranium tetrachloride, copper-I chloride, copper-II chloride, cobalt chloride, chromium trichloride, bisumth trichloride, antimony trichloride, antimony pentachloride, tellurium tetrachloride, arsenic trichloride and arsenic pentachloride.
  • the Bronsted acids and Lewis acids mentioned can be employed both individually and as a mixture of different Bronsted acids, as a mixture of different Lewis acids and as a mixture of Bronsted acids and
  • the process according to the invention is preferably carried out in the presence of sulphuric acid, chlorosulphonic acid, iron-III chloride, zinc chloride or a mixture of these substances. It is particularly preferably carried out in the presence of sulphuric acid or iron-III chloride. It can also be sufficient, for the process according to the invention, for sulphonating agents such as those which technical grade sulphonic acids contain from the preparation process, for example sulphuric acid or chlorosulphonic acid, to be present.
  • the Bronsted acid or Lewis acid is employed in the process according to the invention in an amount of, for example, 0.01 to 20 mol %, preferably of 0.1 to 10 mol %, relative to the sulphonic acid employed.
  • the process according to the invention can be carried out at 20°-300° C., for example at a temperature of 30° to 130° C., preferably 40° to 110° and particularly preferably 50° to 95° C.
  • the pressure is not critical for the ease with which the process according to the invention is carried out, so that the process can be carried out under normal pressure, increased pressure or reduced pressure.
  • the preferred variant is that under normal pressure.
  • Suitable reaction media are those which are inert under the reaction conditions, for example halogenated hydrocarbons, such as chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, pentachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene or dichlorotoluene.
  • Trihalogenomethyl compound employed in excess or the aromatic carboxylic acid chloride formed in the course of the reaction can also serve as the reaction medium.
  • the preferred variant is that without an additional solvent.
  • the aromatic trihalogenomethyl compound For complete conversion of the aromatic sulphonic acid in the process according to the invention, it is necessary to employ at least half an equivalent of the aromatic trihalogenomethyl compound per equivalent of sulphonic acid.
  • the corresponding benzoic acid is thereby formed from the aromatic trihalogenomethyl compound.
  • the aromatic trihalogenomethyl compound in an amount greater than half the equivalent amount, relative to the aromatic sulphonic acid, for example in an equimolar amount.
  • the corresponding benzoyl halide is formed from the aromatic trihalogenomethyl compound.
  • aromatic trihalogenomethyl compound in excess, relative to the aromatic sulphonic acid, for example in an amount of up to 5 equivalents per equivalent of sulphonic acid.
  • the excess aromatic trihalogenomethyl compound serves as a solvent or diluent. An even greater excess is not critical for the process according to the invention, but is less favourable for economic reasons.
  • reaction of the process according to the invention may be represented by the following equations using the reaction of benzenesulphonic acid with benzotrichloride at various ratios of equivalents of aromatic sulphonic acid and aromatic trihalogenomethyl compound as an example: ##STR9##
  • R 17 , R 18 , R 19 , R 17' and R 18' have the meanings of R 1 , R 2 , R 3 , R 1' and R 2' , but the halogenosulphonyl group --SO 2 Hal replaces the sulphonic acid group --SO 3 H and the carboxylic acid halide group --COHal replaces the carboxylic acid group --CO 2 H, and
  • Hal represents chlorine or bromine
  • sulphonyl chlorides are preferably prepared in the process according to the invention: benzenesulphonyl chloride, 2-, 3- and 4-toluenesulphonyl chloride, 2-, 3- and 4-chlorobenzenesulphonyl chloride, benzene-1,3-disulphonyl chloride and 1- and 2-naphthalenesulphonyl chloride.
  • the aromatic trihalogenomethyl compound employed is converted into the corresponding aromatic carboxylic acid compound of the general formula ##STR12## in which U represents hydrogen, ##STR13## wherein V represents --O--, --SO 2 --, --N ⁇ N-- or --CH 2 --,
  • R 20 , R 21 , R 22 , R 20' and R 21' have the scope of meaning of R 4 , R 5 , R 6 , R 4' and R 5' , but the group --COZ appears instead of the trihalogenomethyl group --CHal 3 , and
  • Z represents hydroxyl, chlorine or bromine.
  • the process according to the invention thus simultaneously permits the preparation of an aromatic carboxylic acid or, preferably, its corresponding carboxylic acid halide.
  • an aromatic carboxylic acid or, preferably, its corresponding carboxylic acid halide there is not only a possibility of wide variation with regard to the preparation of the aromatic sulphonic acid halide, but also, by choosing the aromatic trihalogenomethyl compound within the scope of the formula (II) and by choosing in the manner described the ratio of the number of equivalents of aromatic sulphonic acid to aromatic trihalogenomethyl compound, there is the possibility of wide variation with regard to the simultaneous preparation either of an aromatic carboxylic acid or its corresponding carboxylic acid halide, and the substitution of this aromatic carboxylic acid or of its carboxylic acid halide.
  • the starting substances can be added in any desired sequence.
  • the process according to the invention can be carried out batchwise or continuously.
  • the continuous process can be carried out, for example, in a circulatory reactor known to the expert.
  • the starting substances are added at one point of the circulatory reactor, via one or more inlets, whilst at the least some of the reaction mixture is removed again from the reactor, after flowing through the circulatory reactor, at a point shortly before reaching the points of addition again.
  • the reaction mixture removed is worked up by customary methods, for example by fractional distillation. At least some of the residue thereby obtained, which can contain the Bronsted acid or Lewis acid, can be recycled to the circulatory reactor.
  • the Bronsted acid or Lewis acid is added to the aromatic sulphonic acid and the aromatic trihalogenomethyl compound in a stirred apparatus and the mixture is heated to the reaction temperature, whilst stirring, until the evolution of gas has ended.
  • Working up is carried out by known methods, for example by fractional distillation, but also by extraction or other processes.
  • the gaseous hydrogen chloride obtained in the reaction can be collected in a suitable absorption apparatus, for example as aqueous or alcoholic hydrochloric acid. However, it can also be compressed in a pure form and put to further use in this form.
  • aromatic sulphonic acid chlorides which can be prepared according to the invention and the aromatic carboxylic acids simultaneously formed, or the corresponding aromatic carboxylic acid halides, are known to the expert as indispensable intermediate products for a large number of syntheses, for example for esters, amides, hydrazides and other derivatives of sulphonic acids or carboxylic acids for dyestuffs, medicaments and other products.
  • the process according to the invention provides the advantage that no waste acids are formed. Compared with the process using thionyl chloride or phosgene with dialkylformamide catalyst, it provides the advantage that no off-gas mixtures which are difficult to separate are obtained and that no potentially carcinogenic dialkylcarbamic acid chlorides can be formed. Compared with the uncatalysed reaction of aromatic sulphonic acids with trichloromethyl-aromatic compounds, the process according to the invention has the advantage of considerably reduced reaction temperatures and times.
  • a further advantage is that the aromatic trihalogenomethyl compound to be used can be varied greatly according to its availability, the ease of separation of the product mixture and the demand for the aromatic carboxylic acid simultaneously formed or for the corresponding aromatic sulphonic acid halide. If appropriate, the amount of aromatic trihalogenomethyl compound employed can be greatly reduced in comparison with the process of the state of the art.
  • Example 2 after the 0 hour sample, 7.9 g (8 mol %) of sulphuric acid are added and samples are taken, in each case after the same intervals of time, and are investigated by gas chromatography. Table 1 shows the yields after the appropriate reaction times.
  • PhSO 2 Cl denotes benzenesulphonic acid chloride
  • PhCOCl denotes benzoyl chloride
  • PhCCl 3 denotes benzotrichloride. Percentage data in all the examples are relative to the theoretical yield.
  • Examples 5 to 8 were carried out analogously to Example 3, in the same bath size, but in each case a defined amount of catalyst is added to the benzenesulphonic acid.
  • the data can be found in Table 3 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US06/227,445 1980-02-08 1981-01-22 Process for the preparation of aromatic sulphonic acid halides Expired - Lifetime US4349471A (en)

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DE3004693 1980-02-08
DE19803004693 DE3004693A1 (de) 1980-02-08 1980-02-08 Verfahren zur herstellung von aromatischen sulfonsaeurehalogeniden

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US (1) US4349471A (enrdf_load_stackoverflow)
EP (1) EP0034718B1 (enrdf_load_stackoverflow)
JP (1) JPS56125355A (enrdf_load_stackoverflow)
DE (2) DE3004693A1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095150A (en) * 1988-09-13 1992-03-10 Agency Of Industrial Science & Technology Formylated alklbenzenesulfonyl halide compound and process for preparing the same
US20060204812A1 (en) * 2003-03-05 2006-09-14 Hideki Moriyama Aromatic polymer, film, electrolyte membrane and separator

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ294098B6 (cs) * 1996-08-23 2004-10-13 Americanácyanamidácompany Způsob přípravy chloridů azinylových kyselin

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE574836C (de) 1931-07-29 1933-04-20 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von organischen Sulfonsaeurehalogeniden
US3686301A (en) * 1969-05-23 1972-08-22 Lawrence S Kirch Preparation of halosulfonylbenzoyl halides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE758209A (fr) * 1969-10-31 1971-04-29 Hoechst Ag Procede de preparation de chlorures d'acides carboxyliques de la serie benzenique
JPS5524121A (en) * 1978-08-10 1980-02-21 Sanwa Kagaku Kogyo Kk Hydrolysis of benzotrihalide
DE2841541A1 (de) * 1978-09-23 1980-04-03 Bayer Ag Verfahren zur herstellung von gegebenenfalls substituiertem benzoylchlorid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE574836C (de) 1931-07-29 1933-04-20 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von organischen Sulfonsaeurehalogeniden
US3686301A (en) * 1969-05-23 1972-08-22 Lawrence S Kirch Preparation of halosulfonylbenzoyl halides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095150A (en) * 1988-09-13 1992-03-10 Agency Of Industrial Science & Technology Formylated alklbenzenesulfonyl halide compound and process for preparing the same
US20060204812A1 (en) * 2003-03-05 2006-09-14 Hideki Moriyama Aromatic polymer, film, electrolyte membrane and separator
US7511112B2 (en) * 2003-03-05 2009-03-31 Toray Industries, Inc. Aromatic polymer, film, electrolyte membrane and separator
US20090182171A1 (en) * 2003-03-05 2009-07-16 Hideki Moriyama Compound having oxadiazole structure and a dehydration-cyclization method for producing the same
US7868102B2 (en) 2003-03-05 2011-01-11 Toray Industries, Inc. Method for producing a film of an aromatic amide oxadiazole polymer containing an oxadiazole structure and the film so produced

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DE3161451D1 (en) 1983-12-29
DE3004693A1 (de) 1981-08-13
EP0034718B1 (de) 1983-11-23
EP0034718A3 (en) 1982-03-10
JPH0448786B2 (enrdf_load_stackoverflow) 1992-08-07
JPS56125355A (en) 1981-10-01
EP0034718A2 (de) 1981-09-02

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